SU346301A1 - METHOD FOR OBTAINING BIS- (TRIFTOROMETHYL) -KETENIMINES - Google Patents

Description

one

The invention relates to the field of synthesis of bis- (trifluoromethyl) -kentenes, used to modify the properties of wool fabrics to reduce electrification during use.

A known method for producing bis- (trifluoromethyl) -ketenimines by reacting perfluoroisobutylene with N-phenyltriphenylphosphipimine. The disadvantage of this method is the low yield of the target products, as well as the low availability of the starting compounds.

In order to eliminate these drawbacks, a method has been proposed for producing bis- (trifluoromethyl) ketenimines, based on the interaction of perfluoroisobutylene with primary amines in the presence of triethylamine as a catalyst. The preparation of bis- (trifluoromethyl) -kentenes in a new way is carried out in the following way.

To a cooled solution of 3 mol of perfluoroisobutylene in diethyl ether, containing it, a small amount of triethylamine, 1 mol of primary amine was added, and then the reaction mass was maintained at 20-100 ° C. Bis (trifluoromethyl) ketenimines are recovered by distillation. The outputs of the target products 30-90%, depending on the substituent at the nitrogen atom.

Imines are characterized by the presence of absorption in the IR spectra in the range of 2085-2115 slg- (C C N-).

Their structure was also confirmed by the spectra of RMPF (segments in the region from -21 to -23 MD, external standard — trifluoroacetic acid).

Example 1. Obtaining N-methyl-.bis- (trifluoromethyl) -ketape.

CF ,.

 g - g - 1

WITH S YNS

CPH

in a flask with a capacity of 200 ml equipped with a stirrer, an addition funnel, a thermometer, and a reflux condenser cooled with dry ice, 50 ml of abs. ether, 0.1-0.2 ml of triethylamine and 50 g of 90% perfluoroisobutylene (0.224 mol}. The mixture is cooled,

to -78 ° C and a solution of 2.3 g (0.074 mol) of methylamine in 25 ml of ether is added dropwise at such a rate that the temperature of the reaction mass does not exceed 60 to 50 ° C. At the end of the addition, the mixture is heated

while stirring to room temperature, after 2 hours, the resulting solution is loaded into a glass ampoule and heated on a boiling water bath for 7-8 hours. The ampoule after cooling is opened, the contents

rum. The residue after distillation of 2-monohydroperfluoroisobutane and ether is distilled in vacuo. 3.9 g (29%) of N-methyl-bis- (trifluoromethyl) -ketenimine are obtained; m.p. 96-98 ° С (760 mm of mercury.); 54-57 ° C (165 mm Hg. Art.); 1.3344 each.

Found,%: C 31.47; H 1.75. CsHsFsN.

Calculated,%: C 31.41; H 1.57.

PRI mme R 2. Getting S-ethylbis (trifluoromethyl) -ketenimine.

  With NС2П5 CF /

Analogously to example 1, out of 47 g of 63% -peroperfluoroisobutylene (0.15 mol), 2.25 g (0.05 mol) of ethylamine and a few drops of triethylamine in 30 ml of ether, 2.4 g (54%) of N-ethylbis- ( trifluoromethyl) -ketenimine; m.p. PO-112 ° C (760 mm of mercury.); 75-77 ° С (230mmHg); nf 1.3409.

Paideno,%: C, 35.67; P 2.55; N 6.79. SbPZRBY.

Calculated,%: C 35.12; H 2.43; N 6.82.

Example 3. Getting N-cyclohexylbis (trifluoromethyl) -ketenimine

CF,

Analogously to example 1 of 47 (0.15 mol) of 63% perfluorisobutylene, 5 g (0.05 mol) of diclohexylamine and a few drops of triethylamine in 30 ml of ether, 7.6 g (58%) of N-cyclohexylbis (trifluoromethyl) are obtained -ketenimine; m.p. 86-88 ° C (20 mm Hg. Art.);

1.3977 each.

Paideno,%: With 46.33; P 4.16; F 43.94.

SUPR. Calculated,%: With 46,33; P 4.24; F 44.01.

Example 4. Obtaining N-phenyl- (trifluoromethyl) -ketenimine

  b

Vjv41 cly

In 20 ml abs. 14 g (0.05 mol) of 70% perfluorosobutylene is introduced under cooling with ice water with ether containing a few drops of triethylamine. Then 1.5 g (0.016 mol) of aniline is added dropwise. The mixture is left to stand at room temperature for 16 hours and is distilled. 3.6 g (90%) of N-phenylbis (trifluoromethyl) -ketenimine are obtained; m.p. 70-71 ° C (14 mm Hg. Art.); 51 ° С

99

(5 mm Hg. Art.); Pv 1.4462.

Subject invention

Claims (2)

1. A method for producing bis- (trifluoromethyl) ketenimines based on perfluoroisobutylene, characterized in that, in order to increase the yield of the target product, perfluorisobutylene is reacted with primary amines in the presence of triethylamine as a catalyst. 2. A process according to claim 1, characterized in that 3 moles of perfluoroisobutylene are taken per mole of primary amine.